Dyestuffs capable of reaction with textile fibers having acylatable hydrogen atoms



United S tates Patent F 3,117,117 DYESTUFFS CAPABLE OF REACTION WITH TEX- TILE FBERS HAVING ACYLATABLE HYDRO- GEN ATOMS Alistair Howard Berrie and Gerald Booth, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Sept. 7, 1960, Ser. No. 54,354 Claims priority, application Great Britain Sept. 16, 1959 2 Claims. (Cl. 260-162) This invention relates to new dyestuffs and more particularly it relates to new dyestuifs which are capable of entering into reaction with textile fibres containing acylatable hydrogen atoms, such as textile materials comprisingnatural and regenerated cellulose, wool, silk and superpolyarnide fibres.

The present invention provides new dyestuffs capable of reacting with such fibres by virtue of the presence of a halogenobenzenesulphonamido or halogenobenzenecarbonamido group in which the halogen atom is activated by presence of a nitro group.

According to the invention there are provided the new dyestuffs of the formula:

wherein D represents the residue of a coloured compound which contains one or two primary or secondary amino groups and which is linked to A through the nitrogen atom of the amino group or groups, A represents CO or SO Y represents a halogen atom, m represents 1 or 2 and n represents 1' or 2.

As examples of the halogen atoms represented by Y there may be mentioned fluorine, bromine and preferably chlorine atoms.

The residues of the coloured compounds represented by D which contain one or two primary or secondary amino groups may be the residues of any dyestufi series which contains one or two primary or secondary amino groups, but preferably they are residues of dyestufis of the azo, which may be monoazo or polyazo, nitro, anthraquinone or phthalocyanine series which contain one or two primary or secondary amino groups, and which may or may not contain coordinately bound metal such as coordinately bound chromium, copper, cobalt or nickel. It is preferred that the residues of the coloured compounds represented by D also contain at least one water-solubilising group such as carboxylic acid, alkylsulphonarnide, sulphonamide and preferably a sulphonic acid group.

According to a further feature of the invention there is provided a process for the manufacture of the new dyestuffs, as hereinbefore defined, which comprises treating a dyestuif compound ot the formula: D-H, wherein D has the meaning stated, above, with an acid halide of the formula:

wherein A, n and Y have the meanings stated above and X represents a chlorine or a bromine atom.

The process of the invention may be conveniently carried out by stirring the dyestuif compound and the acid halide together in Water or in an organic liquid or in a mixture of water and an organic liquid, preferably in the presence of an acid-binding agent such as sodium carbonate or pyridine, and at a temperature between 0 and 100 C., and filtering sit the dyestuif which is precipi- Patented Jan. 7, 1984 ice tated. If desired sodium chloride or an organic liquid in which the dyestuif is insoluble can be added to ensure complete precipitation of all the dyestuif.

As examples of acid halides which may be used in this process of the invention there may be mentioned 4-chloro 3 nitrobenzene sulphonchloride, 4-chloro-3 :5- dinitrobenzene sulphonchloride, 2-chloro-5-nitrobenzene sulphonchloride, 2-chloro-5-n-itrobenzoylchloride, 2-bromo-S-nitrobenzene sulphonchloride, 4-brotno-3-nitrobenzene sulphonchloride, 4-brorno 3 nit-robenzene sulphonchloride and 2-bromo-5nitrobenzoylchloride.

The dyestuff compounds of the azo series containing one or two primary or secondary amino groups which may be used as starting materials in the above process may be obtained by a variety of methods. One method is to diazotise an aromatic primary amine and couple the diazonium compound so obtained with a coupling component containing a primary or secondary amino group which after the coupling operation remains free to react with the acid halide. As examples of such aromatic primary amines which may be used in this manner to obtain the aminoazo compounds there may be mentioned aniline, 0-, mand p-toluidines, 0-, mand p-anisidines, 0-, mand p-chloroanilines, 2:5-dichloroaniline, etand fi-naphthylamine, 2:5-dimethylaniline, 5-nitro-2- aminoanisole, 4-aminodiphenyl, aniline-2-, 3- and 4-carboxylic acids, 2-arninodiphenylether, 2-, 3- or 4-aminobenzene sulphonamide or sulphonmonomethylor ethyl amides or sulphon-di-methylor ethyl-amides, dehydrothio-p-toluidine monosulphonic acid or dehydrothio-ptoluidine disulphonic acid, -aniline-2-, 3-3 and 4-sulphonic acids, aniline-2:5-disulphonic acid, 2:4-dimethylaniline-6- sulphonic acid, 3-aminobenzotrifluoride-4-sulphonic acid, 4-chloro-5-methyl aniline-2-sul-phonic acid, 5-chloro-4- rmethylaniline 2 sulphonic acid, 3-acetylaminoaniline-6- sulphonic acid, 4-acetylaminoaniline-Z-sulphonic acid, 4- chloroaniline-Z-sulphonic acid, 3z4 dichloroaniline-6-sulphonic acid, 4methylaniline-Z-sulphouic acid, 3-methylaniline-G-su-lphonic acid, 2 2 4-dimethoxyaniline-6-sulphonic acid, 4-methoxyaniline-2sulphonic acid and S-methoxyaniline-2-sulphonic acid, 2:5dichloroaniline-4-sulphonic acid, 2-naphthylamine-4z8- and 6:8-disulphonic acids, 1- naphthylamine-2-, 4-, 5-, 6- or 7-monosulphonic acid, 1-naphthylamine-3:6-disulphonic acid, Z-naph-thylamine- 3:6- and 5:7-disulphonic acids and Z-naphthylamine- 3:6:8-trisulphonic acid, mand p-nitroaniline, 4-nitro-aniline-2-sulphonic acid and 3-nitroaniline-6-sulphonic acid, M- or p-aminoacetanilide, 4-amino-2-acetylaminotoluene- S-sulphonic acid.

As examples of coupling components there may be mentioned Z-aminoand Z-methylamino 5 naphthol-7- sulphonic acids, 2-aminoand Z-methylamino-S-naphthol- 6-sulphonic acids, l-aminoand 1-ethylarninc-8-naphthcl- 6-sulphon-ic acids and the corresponding 3:6- and 4:6-disulphonic acids, l-(3'- or -4-aminobenzoylamino)-8- naphthol-3:6- and 4:6-disulphonic acids, aniline, 0- and m-anisidines, oand m-toluiidines, 2:5-dimethylaniline, 3 amino 4 methoxytoluene, 2:5 dimethoxyaniline, N- methylaniline, N-ethyl-o-toluidine, N-methyl-m-anisidine, 3 -methylamiino4-methoxytoluene, 1- 3 -aminophenyl 3- methyl-, carboxy, and carboethoxy-S-pyrazolones, 1-(4- aminophe-nyl) 3 methyl-, carboxy-, and carboethoxy-5- pyrozolones and l-(4'-amino-3-carboxyphenyl) -3-methyl- S-pyrazolone.

The dyestufi compounds of the azo series used in the process of the invention are not restricted to compounds containing only one azo group. Disazo compounds which may be used may be obtained for example by tetrazotisation of an aromatic diamine containing two primary amino groups and coupling the tetrazo compound so obtained with 2 molecular proportions of one of the abovedefined coupling components or with 1 molecular proportion of each of two of the above-defined coupling components or with one molecular proportion of one of the above-defined coupling components and with one molecular proportion of a coupling component not containing an amino group. As examples of such aromatic diamines there may be mentioned benzidine, 3:3-dimethoxybenzidine, benzidine-Z:2-disulphonic acid, benzidine-3:3'-dicarboxylic acid, benzidine-3:3'-diglycollic acid and 4:4- diaminostilbene-Z 2-disulphonic acid.

Alternatively disazo or polyazo compounds may be obtained by the use of primary aromatic amines or diamines containing azo groups in the above-described processes. As examples of primary aromatic amines or diamines containing azo groups which may be used there may be mentioned 4-aminoazobenzene-4-sulphonic acid, 4'-amino 2 methylphenylazo-Z-naphthalene-4:8-disulphonic acid and 4 amino-3-rnethoxy-Z-methyl-4'-nitro-2'-sulphoazobenzene.

A similar method of obtaining the dyestutf compounds of the azo series which may be used as starting materials comprises coupling a coupling component which optionally contains a primary or secondary amino group with a diazonium compound which contains a primary or secondary amino group. Such diazonium compounds may be obtained by methods known from the art, by the diazotisation of aromatic primary amines containing a second amino group or containing a secondary amino group. As examples of such aromatic primary amines there may be mentioned p-phenylene diamine, 1:4-phenylene diamine 2 sulphonic acid, 1:4-phenylene diarnine-2-carboxylic acid and 1:4-diamino-naphthalene 2 sulphonic acid. As examples of coupling components which may be used in this manner there may be mentioned the coupling components listed above and also ,B-naphthol, 2- naphthol-6- or -7-sulph0nic acid, 2-naphthol-3z6- or 6 :8 disulphonic acids, 1 naphthol 4-sulphonic acid, 1-phenyl 3 methyl-S-pyrazolone, 1:4'-sulphophenyl-3-methyl 5 pyrazolone, 1 (2.:5 dichloro 4' sulphophenyl)-3- methyl 5 pyrazolone, 2-benzoylamino-5-naphthol-7- sulphonic acid, 1-benzylamino-8-naphthol-3:6- or 4:6- disulphonic acid, phenol, p-cresol, acetoacetanilide and acetoacet-2-methoxyanilide-S-sulphonic acid.

A further method of obtaining the dyestuff compounds of the azo series which may be used as starting materials is to treat an azo or polyazo compound containing one or two acylamino groups with aqueous acid or aqueous alkali in order to cause hydrolysis of the acylamino group or groups. Such azo or polyazo compounds may be obtained from aromatic primary amines and/or coupling components containing acylamino groups. As examples of such aromatic primary amines, in addition to the acylaminoarylamines mentioned above, there may be mentioned monoacetylbenzidine, 4-amino l acetylaminonaphthalene 6 sulphonic acid, 4-amino-4-acetylaminodiphenyl 3 sulphonic acid, 4-amino-4'-acetylaminostilbene 2:2'-disulphonic acid, and as examples of coupling components there may be mentioned 'Z-acetylamino- 5 naphthol 7-sulphonic acid, Z-acetylmethylamino-S- naphthol 7 sulphonic acid, 2-acetylaminoand acetylmethylamino 8 naphthol-6-sulphonic acids, and 1- acetylamino-8-naphthol-3:6- and 4:6-disulphonic acids.

Yet a further method of obtaining the dyestutf compounds of the azo series which may be used as starting materials is to treat an azo or polyazo compound containing one or two nitro groups attached to an aromatic ring, with a reducing agent for example sodium sulphide, sodium hydrogen sulphide or sodium dior polysulphides, known to be capable of reducing an aromatic nitro compound to the corresponding amino compound.

As examples of dyestuff compounds of the anthraquinone series which may be used as starting materials for making the new dyestuffs of the invention there may be mentioned those containing one or two primary or secondary amino groups as substitutents in an alkylamino or an arylamino group attached to an alpha-position of the anthraquinone nucleus. As examples there may be mentioned 1 amino 4 (4'-aminoanilino)anthnaquinone 2:3'-disulphonic acid and the corresponding 2:3:5- and 2:3z 6-trisulphonic acids, 1 amino 4-(4"-amino-4'- benzoylaminoaniline) anthraquinone 2:3-disulphonic acid and the corresponding :2:3':5-trisulphonic acid, 1- amino 4 [4' (4"-aminophenylazo)-anilino]-anthraquinone 2:2":5 trisulphonic acid, 1 amino 4 (4' amino 3' carboxyanilino )anthraquinone 2:5 disulphonic acid, 1 amino 4 (3'-aminoanilino)anthraquinone 2:4':5 trisulphonic acid and the corresponding 2:4 disulphonic acid, 1 amino 4 [4'-(4-arninophenyl-)anilino]anthraquinone 2:3:5 trisulphonic acid, 1 amino 4 (4' methylarnino)anilino anthraquinone 2:3 disulphonic acid and the corresponding 2:3':5 trisulphonic acid, 1-amino-4-(4'-n-butylamino) anilino-anthraquinone-Z:3' disulphonic acid, 1 amino- 4 (4 methylamino 3 oarboxyanilino-)anthraquinone- 2 sulphonic acid and l amino 4-(3'-beta-hydroxyethylamino-)anilino anthraquinone 2:5 disulphonic acid, 1:4 aminoanilinoanthraquinone 2:3'-disulphonic acid and l amino 4 (4-amino 2'-methoxyanilino)- anthraquinone-Z 3 '-disulphonic acid.

These starting materials of the anthraquinone series may themselves be obtained from anthraquinone compounds, containing a halogen atom or a nitro group attached to the appropriate alpha-position of the anthraquinone nucleus, or from the leuco derivative of a 1:4- dihydroxy, -diaminoor -amino-hydroxy-anthraquinone, by interacting the appropriate anthraquinone compound with at least one molecular proportion of an aliphatic or an aromatic diamine.

Dyestuif compounds of the phthalocyanine series which may be used as starting materials for making the new dyestuffs of the invention are those containing one or two primary or secondary amino groups. Preferred dyestuif compounds of the phthalocyanine series are metal-containing phthalocyanines, in particular copper phthalocyanine which contains at least one sulphonic acid group and one or two primary or secondary amino groups. The primary or secondary amino group or groups may be attached directly to the benz-rings of the phthalocyanine nucleus or they may be attached thereto through a divalent bridging radical for example -phenylene-, -CO-phenylene-, SO -phenylene-, -NH-phenylene-, S phenylene-, O phenylene-, -CH S-phenylene-, CH O phenylene-, CH -phenylene-, SCH -phenylene-, -SO CH -phenylene-, SO2NR phenylene-CH SO' NR-arylene-, NRCO-phenylene, -NRSO -phenylene-, SO O-phenylene-, CI-I CH NR-phenylene, CH NH.CO'- phenylene-, -SO NR-alkylene-, CH NR alkylene-, CONR-phenylene-Cl-I CONR-arylene-, SO and CO-. In the above divalent bridging radicals, R stands for hydrogen, alkyl or cycloalkyl, arylene stands for an aromatic divalent bridging radical wherein the terminal valence bonds may be attached to the same or different nuclei, and alkylene stands for an aliphatic divalent radical which may include hetero-atoms such as nitrogen as well as carbon in the chain of atoms, for example it may stand for the radical I and the phenylene groups may be substituted, for example by halogen, alkyl and alkoxy.

As examples of aromatic divalent bridging radicals denoted by arylene there may be mentioned aromatic nuclei, for example a benzene nucleus, a napthalene nucleus, an acridine nucleus and a carbazole nucleus, which nuclei may bear further substituents, and radicals of the formula:

wherein the benzene rings may bear further substituents and wherein D stands for a bridging group, for ex- As specific examples of dyestufi compounds of the phthalocyanine series which may be used in the process of the invention there may be mentioned copper phthalocyanine 4 N (4 amino 3 sulphophenyl) sulphonamide 4':4":4 trisulphonic acid, cobalt phthalocyanine 4:4 di N (3' amino 4' sulphophenyl-)carbonamide 4":4 dicarboxylic acid and copper 4-(4- amino-3 '-sulphob enzoylphth alocyanine.

There may also be used mixtures of aminophthalocyanines, for example there may be used a mixture of approximately equal parts of copper phthalocyanine-N- (4 amino 3 sulphophenyl-)sulphonamide trisulphonic acid and copper phthalocyanine di-[N-(4-amino-3-sulphophenyl-) sulphonamide] disulphonic acid.

The aminophthalocyanines used which contain a sulphonic acid can be manufactured either by the sulphonation of known phthalocyanines containing primary or secondary amino groups or by synthesis from mixtures of phthalic acid derivatives and sulphonated phthalic acid derivatives. Thus treatment with a sulphonating agent for example oleum such as 20% solution of sulphur trioxide in sulphuric acid of the amines described in United Kingdom specifications Nos. 569,200 and 589,118 gives suitable aminophthalocyanines. The aminop thalocyanine compounds so obtained are those containing the divalent bridging radicals -phenylene-, --CO-phenylene-, -SO -phenylene-, NH-phenylene-, S-phenylene-, --O-phenylene, CH S-phenylene-, CH O-pheny1ene, CH -phenylene-, -SCH -phenylene and SO CH phenylene.

Those aminophthalocyanine compounds which contain the divalent bridging radicals mentioned in the last paragraph and also those containing NRCO-phenylene-, SO NR-phenylene-, NRSO -phenylene-, and S 0- phenylene linkages as bridging radicals may be obtained by heating together suitable derivatives of sulphonated phthalic acid and the substituted phthalic acids mentioned in the aforesaid United Kingdom specifications Nos. 569,200 and 589,118 by the general methods known to be used for the manufacture of phthalocyanines from suitable phthalic acid derivatives, for example, by heating together a mixture of 4-sulphophthalic anhydride and 4-o-nitrobenzoylphthalic anhydride, urea, cupric chloride, and ammonium molybdate in o-clichlorobenzene at about 150 C.; those which contain the CH linkage may be obtained by sulphonation of the primary and secondary amines of United Kingdom specifications Nos. 717,137 and 724,212; those which contain the CH NR-phenylene-linkage may be obtained by reacting a primary (or secondary N-alkyl or cycloalkyl-)nitroaniline with a phthaiocyanine containing chloromethyl and sulphonic or carboxylic acid groups obtained by chloromethylation of a phthalocyanine sulphonic or carboxylic acid, and reducing the product so obtained for example with sodium sulphide or by reacting a chloro-methyl phthalocyanine with for example a diaminobenzenesulphonic acid or -carboxylic acid; those which contain the SO NR-alkylenelinkage may be obtained by reacting a phthalocyanine containing chlorosulphonyl groups with a monoacetyl alkylene diamine in the presence of Water, and treating the product so obtained (which contains both sulphonamide and sulphonic acid groups) with aqueous alkali to hydrolyse the acetylamino group; those which contain the SO NR-phenyieneCH -linkage may be obtained in a similar manner by using an amino-N-benzylacetamide in place of the monoacetylalkylene diamine; those which contain the -CH .NR-alkylenelinkage may be obtained G Y i by reacting a phthalocyanine containing chloromethyl and sulphonic or carboxylic acid groups with a monoacetyl alkylene diamine and treating the product so obtained with aqueous alkali to hydrolyse the acetylamino groups; those containing a direct link, so that the amino group is attached directly to the phthalocyanine nucleus, may be obtained by sulphonating the amino-phthalocyanines described in United Kingdom specification No. 529,847 or where a starting material containing less than 4 amino groups attached to the phthalocyanine nucleus is desired, it may be obtained by heating together a mixture of suitable carboxyor sulphophthalic acid derivatives with one of the substituted phthalic acid derivatives used as starting materials in United Kingdom specification No. 529,847 under conditions known to be used for the manufacture of phthalocyanines from phthalic acid derivatives, for example by heating the anhydrides with urea and a catalyst for example ammonium molybdate in an organic solvent for example o-dichlorobenzene, and reducing the nitro-phthalocyanine sulphonic or carboxylic acid or hydrolysing the acylaminophthalocyanine sulphonic or carboxylic acid so obtained by known methods for the conversion of aromatic nitro or acylamino compounds to the corresponding amines; and those containingthe CO.NR- phenylene-linkage may be obtained by reacting a phthalocyanine compound containing carboxylic acid chloride groups with a diaminobenzene sulphonic acid or carboxylic acid or with an aminobenzene sulphonic acid or an aminobenzoic acid which also contains a nitro group and reducing the nitro compound so obtained; and those containing the -CONR-phenyleneCH -linkage may be obtained by reacting a phthalocyanine compound containing carboxylic acid chloride groups with an N-(amino-benzyl-)acetamide and subsequently hydrolysing the product so obtained with aqueous alkali.

Suitable dyestufi compounds of the nitro series which may be used as starting materials for making the new dyestuffs of the invention are those of the formula:

XI NOB-l R where B stands for a naphthalene or benzene nucleus which may be further substituted wherein the nitrogen atom N is in the ortho position to the nitro group, X stands for hydrogen or for a hydrocarbon radical which may be substituted, R stands for hydrogen or for an organic radical attached to the nitrogen through a carbon atom, provided that X and R are not both hydrogen, and wherein R may be connected to X when X is a hydrocarbon radical or to B, in the ortho position to the nitrogen atom, N, to form a heterocyclic ring, and which contain one or two primary or secondary amino groups.

As specific examples of dyestufi compounds of the nitro series which may be used there may be mentioned sulphonic acid derivatives of substituted diphenylamines and phenylnaphthylamines, for example 2:4-dinitro-4'-amino diphenylamine-3'-sulphonic acid, 2-nitro-3-amino-4'-carboxydiphenylamine-4-sulphonic acid, 2-nitro-4-(p-amino anilino-)diphenyiamine-3':4-disulphonic acid, 2-nitro-4 methylaminodiphenylamine-3' 4-disulphonic acid, Z-nitro- 4' methylamino 4 sulphon-betahydroxyethylamidodiphenylamine-3'-sulphonic acid, 2-nitro-4-methylamino-4- carboxydiphenylamine-3-sulphonic acid, 2-nitro-4'-amino-1'naphthylphenylamine-4:6'-disulphonic acid and 1:5- dinitro 2:6 di (4-amino-3-sulphoanilino-)napthalene. These sulphonic acid derivatives may conveniently be obtained by the reaction of the appropriately substituted o-nitrochloro-benzene or -naphthalene with the appropriately substituted diamine, (at least one of the reagents containing a sulphonic acid group) in aqueous or alcoholic media in the presence of an acid-binding agent for example calcium carbonate at elevated temperatures for example at a temperature of C.

As examples of dyestufif compounds containing one or two primary or secondary amino groups which can be used in the process of the invention there may be mentioned the compounds of the following classes without, however, limiting the classes to those specifically described. In the following classes R denotes a primary or secondary amino group.

(1) Monoazo compounds of the formula:

Ma a

J he; wherein D represents a mono or di-cyclic aryl radical which is free from azo groups and primary and secondary amino groups, R is preferably attached to the 6-, 7- or 8- position of the naphthalene nucleus, and which may contain a sulphonic acid group in the 5- or 6-position of the naphthalene nucleus.

D may represent a radical of the naphthalene or benzene series which is free from azo substituents, for example a stilbene, diphenyl, benzthiazolylphenyl or diphenylarnine radical. Also in this class are to be considered the related dyestuffs in which R instead of being attached to the naphthalene nucleus, is attached to a benzoylarnino or anilino group which is attached to the 6-, 7- or 8-position of the naphthalene nucleus.

Particularly valuable dyestuffs are obtained from those wherein D represents a sulphonated phenyl or naphthyl radical, especially those which contain a SO H group in ortho position to the azo link; the phenyl radical may be further substituted for example, by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetylamino and alkoxy radicals such as methoxy.

(2) Disazo compounds of Formula I, wherein D stands for a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the NHR group, and optionally by sulphonic acid as in class 1.

(3) Monoazo compounds of the formula:

Formula 11 wherein D stands for an at most dicyclic aryl radical as described for class 1 and is preferably a disulphonaphthyl or a stilbene radical, and the benzene nucleus may contain further substitutents such as halogen atoms, or alkyl, alkoxy, carboxylic acid and acylamino groups.

(4) Monoor disazo compounds of the formula:

wherein D represents an arylene radical such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series, or, preferably, an at most dicyclic arylene radical of the benzene or naphthalene series, and X represents the radical or a naphthol sulphonic acid or the radical of an enolised or enolisable ketomethylene compound (such as an acetoacetarylide or a S-pyrazolone) having the OH group to the azo group. D preferably represents a radical of the benzene series containing a sulphonic acid group.

() Monoor disazo compounds of the formula:

D1N:NK2 R' Formula IV wherein D represents a radical of the types defined for D in classes 1 and 2 above and K represents the radical of an enolisable ketomethylene compound (such as an acetoacetarylide or a S-pyrazolone) having the OH group in zx-pOSiti0I1 to the azo group.

(6) The metal complex, e.g. the copper, chromium and cobalt complex, compounds of those dyes of Formulae I, III and IV (wherein D K and K have all the respective meanings rated) which contain a metallisable (for example, a hydroxyl, lower alkoxy or carboxylic acid) group ortho to the azo group in D Formula I Formula HI 8 (7) Anthraquinone compounds of the formula:

i i" C 4 son: I,

0 l IHZR wherein the anthraquinone nucleus may contain an additional sulphonic acid group in the 5-, 6-, 7- or 8-position and Z represents a bridging group which is preferably a divalent radical of the benzene series, for example phenylene, disphenylene or 4,4-divalent stilbene or azobenzene radicals. It is preferred that Z should contain one sulphonic acid group for each benzene ring present. (8) Phthalocyanine compounds of the formula:

(solNHZ R') wherein Pc represents the phthalocyanine nucleus preferably of copper phthalocyanine, w represents a hydroxy and/or an amino or substituted amino group, Z represents a bridging group, preferably an aliphatic, cycloaliphatic or aromatic bridging group, n and In each represents l, 2 or 3 and may be the same or different provided that n+m is not greater than 4.

IN CLASS 1 6-amino-l-hydroxy-2-(2 sulphophenylazo)naphthalene- 3-sulphonic acid,

-methylamino 1 hydroxy-2-(4'-acetylamino-2'-su1phophenylazo)naphthalene-3-sulphonic acid,

S-arnino-l-hydroxy-Z-(Z sulphophenylazo)naphthalene- 3z6-disulphonic acid,

S-amino l hydroxy-Z-(4'-chloro-2-sulphophenylazo)- naphthalene-3 :5 -disulphonic acid,

'7 amino 2 (2':5'-disulphophenylazo)-l-hydroxynaphthalene-S-sulphonic acid,

7-methylamino-2-(2' sulphophenylazo)-l-hydroxynaphthalene-3-sulphonic acid,

7-methylamino-2-(4'-methoxy 2' sulphophenylazo)-1 hydroxynaphthalene-El-sulphonic acid,

8-(3' aminobenzoylamino)-1-hydroxy-2-(2'-sulphophenylazo -naphthalene-3 -disulphonic acid,

S-amino-l-hydroxy-Z :2 azonaphthalene-l' 3 5 6-tetrasulphonic acid,

S-amino 1 hydroxy-Z:2'-azonaphthalene-1':3:5'-trisulphonic acid,

6-amino l hydroxy-Z:2'-azonaphthalene-l:3:5-trisulphonic acid,

6-methylamino 1 hydroxy-Z:2'-azonaphthalene-l':3:5-

trisulphonic acid,

7-amino-l-hydroxy-2 :2 azonaphthalene- 1 3-disulphonic acid,

8-amino-1-hydroxy-2-(4' hydroxy-3-carboxyphenylazo)- naphthalene-3 6-disulphonic acid,

6-amino-1-hydroxy-2-(4 hydroxy-3'-carboxyphenylazo)- naphthalene-3 :5 -disulphonic acid.

IN CLASS 2 S-amino-l-hydroxy-Z-[4-(2" sulphophenylazo)-2-methoxy-5'-methylphenylazo]naphthalene 3 :6 disulphonic acid,

8 amino 1 hydroxy-Z-[4-(4"-methoxyphenylazo)-2'- carboxyphenylazo]naphthalene-3 :6-disulphonic acid, S-amino 11 hydroxy-Z-[4'-(2"-hydroxy-3":6"-disulpho- 1"-naphthy-lazo) 2' carboxyphenylazo] naphthalene- 3:6-disulphonic acid,

4:4 bis(8-arnino-1-hydroxy-3":6"-disulpho-2"-naphthylazo -3 3 '-'dimethoxydiphenyl,

G-amino-1-hydroxy-2-[4'-(2 sulphophenylazo)-2'-methoxy-5-methylphenylazo] naphthalene 3 :5 disulphonic acid,

9 IN CLASS 3 2-(4-amino 2 methylphenylazo)naphthalene-4:8-disulphonic acid,

2-(4 amino-2'-acetylaminophenylazo)naphthalene-5:7-

disulphonic acid,

4-nitro-4 (4" methylaminophenylazo)stilbene-2:2-disulphonic acid,

4 nitro-4'-(4"-amino-2"-methyl-5"-methoxyphenylazo)- stilbene-2 :2-disulphonic acid,

4-amino-4' (4" methoxyphenylazo)stilbene-2:2 disul phonic acid,

4-amino-2-methy1azobenzene-2' '-disulphonic acid.

IN CLASS 4 1 (2'25 dichloro 4' sulphophenyl)-3-methyl-4-(3"- amino-4"-sulphophenylazo) -5-pyrazolone,

1-(4-sulphophenyl) 3 carboxy-4-(4-amino-3"-sulphophenylazo) -5-pyrazolone,

1-(2-methyl-5'-sulphophenyl) 3 methyl-4-(4-amino- 3-sulphophenylazo -5-pyrazolone,

1-(2'-sulphophenyl) 3 methyl-4-(3"-amino-4"-sulphoheny'lazo -5-pyrazolone,

4-amino-4'-(3"-methyl 1" phenyl-4"-pyrazol-5"-onylazo) stilbene-2 2'-disulphonic acid,

4-amino-4-(2-hydroxy-3:6"-disulpho 1" naphthylazo) -stilbene-2 2'-disulphonic acid,

S-acetylamino 1 hydroxy-2-(3'-amino-4-sulphophenylazo)naphthalene-3 6-disulphonic acid,

7 (3'-sulphophenylamino) 1 hydroxy-2-(4'+amino-2- carboxyphenylazo)naphthalene-3-sulphonic acid,

8 phenylarnino l-hydroxy-Z-(4-amino-2-sulphopl1enylazo) naphthalene-3 S-disulphonic acid,

6-acetylarnino 1 hydroxy-2-(5-ainino-2-sulphophenylazo)naphthalene-Za-sulphonic acid.

IN CLASS 5 1-(3-aminophenyl) 3 methyl-4-(2:S'-disulphophenylazo -5-pyrazolone,

1-(3 aminophenyl)-3-carboxy-4-(2'-carboxy-4'-sulphophenylazo -5-pyrazolone,

4 amino-4-[3"-methyl-4"-(2"':5'-disulphophenylazo)- 1"-pyrazol-5 -onyl] stilbene-Z 2'-'disulphonic acid,

1-(3 aminophenyl)-3-carboxy-4- [4"-(2":5-disulphophenylazo)-2"-methoxy 5" methylphenylazo]-5-pyrazolone.

IN CLASS 6 The copper complex of 8-amino-1-hydroxy-2-(2'-hydroxy- 5 '-sulphophenylazo naphthalene-3 6-disulphonic acid,

The copper complex of 6-amino-1-hydroxy-2-(2'-hydroxy- 5-su-lphophenylazo)naphthalene-3-sulphonic acid,

The copper complex of 6-amino-1-hydroxy-2-(2-l1ydroxy- 5 -sulphophenylazo naphthalene-3 5 disulphonic acid,

The copper complex of S-amino-l-hydroxy-Z-(2-hydroxy- 3-chloro 5' sulphophenylazo) naphthalene-3:6-disulphonic acid,

The copper complex of 6 methylamino 1 hydroxy-Z- (2' carboxy 5 sulphophenyl'azo)naphthalene-3-sulphonic acid,

The copper complex of 8-amino-1-hydroxy-2-[4'-(2-sulphophenylazo) 2 methoxy 5 methylphenylazo]- naphthalene-3 6-disulphonic acid,

The copper complex of 6-an1ino-1 hydroxy-2-[4 (2":5"- disulphophenylazo) 2 methoxy 5 methylphenylazo] naphthalene-3 :S-disulphonic acid,

The copper complex of 1-(3-amino-4-sulphophenyl)-3- methyl 4 [4"-(2":5'-disulphophenylazo)-2-methoxy-S "-methylphenylazo] -5 -pyrazo-lone,

The copper complex of 7-(4-amino-3'-sulphoanilino)-1- hydroxy-2[4"-(2:5 disulphophenylazo)-2-methoxy-5-methylpheny1azo]naphthalene-B-sulphonic acid,

The copper complex of 6-(4'-amino-3-sulphonilino)-1- hydroxy 2 (2"-carboxyphenylazo)naphthalene-3-sulphonic acid,

The 1:2-chromium complex of 7-an1ino-6'-nitro-1:2-dihydroxy-Z: 1'-azonaphtha-lene-3 :4-disulphonic acid,

The 1:2-chromium complex of 6-amino-1-hydroxy-2-(2'- carboxyphenylazo) naphthalene-3-sulphonic acid,

The lzl-chromium complex of 8-amino-1-hydroxy-2-(4'- nitro 2' hydnoxyphenylazo)naphthalene 3:6 disulphonic acid,

The 1:2-cobalt complex of 6-(44amino-3-sulpl1oanilino)- 1-hydroxy-2-(5-chloro 2" hydroxyphenylazo)naphthalene-3-sulphonic acid,

The 1:2-chromium complex of 1 (3f amino-4-sulpho phenyl) 3 methyl-4-(2 hydroxy-4-sulpho-1-naphthylazo -5 -pyrazolone,

The 1:2-chromium complex of 7-(4'-sulphonilino)-1-hydroxy-2-(4" amino 2 carboxyphenylazo)naphthalene-3-sulphonic acid,

The 1:2-chromium complex of l-(3-aminophenyl) -3- methyl 4 (4"-nitro-2"-carboxyphenylazo)-5-pyrazolone.

IN CLASS 7 1 amino-4-(3-amino-4-t,ulphoanilino)anthraquinone-Z- sulphonic acid,

1-amino-4-(4'-amino 3 sulphoanilino)anthraquinone- 2:5-disulphonic acid,

1 amino-4-[4'-(4-amino-3-sulphophenyl)anilino] anthraquinone-Z 5 disulphonic acid,

14amino-4-[4-(4"-arnino-2" sulphophenylazo)anilino]- anthraquinone-Z S-disulphonic acid,

1-amino-4-(4 methylamino-3'-sulphoanilino)anthraquinone-Z-sulphonic acid.

IN CLASS 8 3 (3-amino-4'-sulphophenyl)sulphamyl copper phthalo cyanine-tri-3-sulphonic acid,

Di 4 (3-amino 4 sulphophenyl)sulphamy-1 copper phthalocyanine-di-4-sulphonic acid,

3 (3' iaminophenylsulphamyl) 3 sulph'amyl copper phthalocyanine-di-3-sulphonic acid,

According to a further feature of the invention there is provided a modified process for the manufacture of the new dyestuffs of the invention wherein D represents the residue of an azo dyest-utf containing one or two primary or secondary amino groups, which comprises diazo tising a primary aromatic amine, or the corresponding sulphamic acid, and coupling the diazo compound so obtained with a coupling component, the primary aromatic amine and the coupling component containing one or two groups, as hereinbefore defined.

This modified process of the invention may be conveniently brought about by adding sodium nitrite to a solution or suspension of the primary aromatic amine, which may be an aminoazo compound (or the corresponding sulphamic acid), in a dilute aqueous solution of hydrochloric acid, adding the resulting solution or suspension of the diazo compound to a solution of the coupling component and filtering off the dyestuff which is precipitated. If necessary sodium chloride can be added to ensure complete precipitation of all the azo dyestuif.

The primary amine, or the corresponding sulphamic acid, used in this modified process of the invention can be a member of any of the known series of diazotisable primary amines of the benzene or naphthalene series which optionally contains an ary-l'azo group. The coupling component used in this modified process of the invention can be a member of any of the known series of coupling components, but preferably it is a coupling component of the acylacetarylide, S-pyrazolone, phenol, naphthol or arylamine series.

1 1 Those coupling components which contain a group of the formula:

(NO ln as hereinbefore defined, may themselves be obtained by treating the corresponding coupling component containing a primary or secondary amino group with an acid halide, as he-reinbefore defined.

'l hose primary amines, or the corresponding sulphamic acids, which contain a group of the formula:

may themselves be obtained by treating the corresponding primary amine, or the corresponding sulphamic acid, and containing a primary or secondary amino group with an acid halide as hereinbefore defined.

A preferred class of the new dyestuffs of the invention are those dyestuffs which contain at least one watersolubilising group, which is preferably a sulphonic acid group, and it is preferred that the CO or -SO group represented by A and the nitro group or groups are attached to the benzene ring in ortho or para position to the halogen atom represented by Y.

The new dyestuffs of the invention are valuable for colouring natural and artificial textile materials for example cellulose textile materials such as cotton, viscose rayon and linen, and woollen textile materials, whereby the textile materials are coloured in a wide range of shades which possess good fastness to Wet treatments such as Washing.

The dyestufis may be applied to the textile materials by either a dyeing or printing process. In the case of cellulose textile materials it is preferred to apply the dyestuffs to the textile materials in conjunction with a treatment with an acid-binding agent, which may be carried out before, after or during the application of the dyestuif. As examples of such acid-binding agents there may be mentioned sodium carbonate, trisodium phosphate, sodium silicate and sodium or potassium hydroxide, or there may be used substances such as sodium bicarbonate or sodium trichloroacetate which on heating or steaming liberate an acid-binding agent.

The new dyestuffs of the invention are particularly valable for colouring woollen textile materials and this may be conveniently brought about by applying the dyestuffs from a mildly alkaline, neutral or acid dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that is to say the pH of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process by the addition of acids or acid salts, or alkalis or alkaline salts. For example dyeing may be started at a dyebath pH of about 3.5 to 5.5 and raised during the dyeing process to about 6.5 to 7.5 or higher if desired.

The invention is illustrated but not limited by the following examples in which parts and percentages are by weight:

Example 1 A mixture of 4.6 parts of 4-amino-2-hydroxy-5'-methylazobenzene, 150 parts of acetone and 100 parts of water are stirred at a temperature of 5 to C. and a solution of 5.2 parts of 4-chloro-3-nitrobenzene sulphonchloride in parts of acetone is added during 1 hour, maintaining the mixture neutral by addition of sodium carbonate. The mixture is stirred for 16 hours at a temperature of 10 to 20 C., then filtered and the product on the filter is washed with Water and dried.

The new dyestulf so obtained is a yellow-brown powder which dyes polyamide textile materials in yellow shades of good washing fastness.

Example 2 A solution of 10 parts of 4-chloro-3-nitrobenzene sulphonchloride in 12 parts of acetone is added during 3 hours to a solution of 15.8 parts of the trisodium salt of 6 methylamino 1 hydroxy 2:2 azonaphthalene- 1':3:5-trisulphonic acid and 1 part of the disodium salt of dinaphthylmethane disulphonic acid, the temperature being maintained at 20 C. and the mixture is stirred for 16 hours, the pH being kept at 7 to 8 by the addition of sodium carbonate. The mixture is then filtered and sodium chloride is added to the filtrate to precipitate the dyestuff. The precipitate is filtered off, washed with water and then with acetone and dried.

The new dyestuff so obtained is a powder which dyes cotton, viscose rayon and wool in orange shades of good fastness to washing.

Example 3 A solution of 10 parts of 4-chloro-3:S-dinitrobenZene sulphonchloride in parts of acetone is added during 4 hours to a solution of 6.3 parts of the trisodium salt of 6- methylamino 1 hydroxy 2:2 azonaphthalene- 1':3:5-trisulphonic acid and 0.5 part of the disodium salt of dinaphthylmethane disulphonic acid, the temperature being maintained at 20 C., and the mixture is stirred for 48 hours, the pH being kept at 7 to 8 by the addition of sodium carbonate. The mixture is then filtered and sodium chloride is added to the filtrate to precipitate the dyestuff. The precipitate is filtered 01f, washed with brine and dried.

The new dyestuff so obtained is a yellow brown powder which dyes cotton, viscose rayon and wool in orange shades of good fastness to washing.

Example 4 A solution of 12 parts of 4-chloro-3-nitrobenzene sulphonchloride in 80 parts of acetone is added to a solution of 6.35 parts of the trisodium salt of l-amino-4-(4- aminoanilino) anthraquinone-2z3':S-trisulphonic acid in 70 parts of Water, and the resulting mixture is stirred at 20 C. until no further additions of a 10% aqueous solution of sodium carbonate are required to maintain the pH of the mixture at 7. 20 parts of sodium chloride are then added and the precipitated dyestufi is filtered off, washed with a 20% aqueous solution of sodium chloride and dried.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields blue shades possessing good fastness to wet treatments.

Example 5 A solution of 7.8 parts of 4-chloro-3-nitrobenzene sulphonchloride in 20 parts of acetone is added, during 2 hours, to a solution of 15.6 parts of the sodium salt of copper phthalocyanine 3-sulphon-N-(3-amino-4'-sulphop'heri'yDamine sulphonic acid and 1 part of the disodium salt of dinaphthylmethane disulphonic acid in 300 parts of water, and the resulting mixture is stirred for 20 hours at 20 C., 22 parts of a 2 N aqueous solution of sodium carbonate being gradually added to maintain the pH of the mixture between 7 and 8. 500 parts of acetone, 15.5 parts of 4-chloro-3-nitrobenzene sulphonchloride and 57 parts of a 2 N aqueous solution of sodium carbonate are then added and the mixture is stirred for a further 3 hours at 20 C. The resulting solution is then evaporated until the volume is 400 00s., sodium chloride is added until the solution contains 15% by weight of sodium chloride and the precipitated dyestuff is filtered off and dried.

When applied to wool from a slightly acid dyebath '13 the dyestutf yields greenish-blue shades possessing very good fastness to washing.

Example 6 7 parts of a concentrated aqueous solution of hydrochloric acid are added to a solution of 1.94 parts of 6-nitro-2-aminophenol-4-sulphonamide and 1.2 parts of sodium hydroxide in 50 parts of water. The resulting mixture is cooled to C. and a solution of 0.58 part of sodium nitrite in 4.2 parts of water is then added, the temperature of the mixture being maintained between 0 and C. by external cooling. Sodium bicarbonate is then added until the mixture is neutral to Congo red and the mixture is added to a solution of 3.31 parts of l- (4'-chloro-3'-nitrobenzenesulphonyl) amino-7 naphthol, 0.8 part of sodium hydroxide and 2 parts of sodium carbonate in 150 parts of water, the temperature of the mixture being maintained between 0 and 5 C. by external cooling. The mixture is stirred for 4 hours at this temperature and the precipitated dyestulf is then filtered off, washed with a 5% aqueous solution of sodium bicarbonate and dried.

When applied to woollen textile materials by the metachrome or afterchrome process the dyestuff yields grey shades possessing food fastness to washing.

Example 7 In place of the 1.94 parts of 6-nitro-2-aminophenol- 4-sulphonamide used in Example 6 there are used 154 parts of 4-nitro-2-aminophenol-4-sulphonamide when a similar dyestuff is obtained.

The 1 (4' chloro-3'-nitrobenzenesulphonyl)amino-7- naphthol used in Examples 6 and 7 may be obtained as follows:

15.9 parts of 1-amino-7-naphthol are dissolved in a mixture of 150 parts of water and parts of a concentrated aqueous solution of hydrochloric acid and sodium acetate is then added until the solution is no longer acid to Congo red. The solution is cooled to 0 C., a solution of 52 parts of 4-chloro-3-nitrobenzene sulphonchloride in 55 parts of acetone is added and the mixture is stirred for hours at a temperature between 0 and 5 C., 26 parts of sodium acetate crystals being gradually added to maintain the mixture neutral to Congo red. 77 parts of a 32% aqueous solution of sodium hydroxide are added and the mixture is filtered. 47 parts of a concentrated aqueous solution of hydrochloric acid are added to the filtrate and the'precipitated l-(4'-chloro-3-nitrobenzenesulphonyl)amino-7-naphthol is filtered off, washed with water and dried. The product melts at 122 and 124 C.

Example 8 A mixture of 5.18 parts of the dyestuil of Example 6, 1.41 parts of chromium acetate, 90 parts of fi-ethoxyethanol and 100 parts of water is stirred at the boil under a reflux condenser for 1% hours. 5 parts of an aqueous solution of sodium potassium chromosalicylate (which is obtained as described in Example 2 of British specification No. 787,305) are then added and the mixture is stirred at the boil for a further hour. The resulting solution is filtered and the filtrate is poured into 300 parts of a 20% aqueous solution of sodium chloride. The precipitated dyestutf is then filtered off, washed with a 5% aqueous solution of sodium chloride and dried.

On analysis the dyestuff is found to contain 0.98 atom of organically bound chlorine for each azo group present in the dyestufi'.

When applied to wool from a slightly acid dyebath the dyestuff yields grey shades possessing good fastness to washing.

Example 9 A mixture of 543 parts of the dyestuff of Example 7, 1.56 parts of chromium acetate, 90 parts of B-ethoxyethanol and 100 parts of water is stirred for 1 hour at 14 the boil under a reflux condenser. The resulting solution is then cooled to 20 C., filtered and the filtrate is poured into 400 parts of a saturated aqueous solution of sodium chloride. The precipitated dyestufi is then filtered oil, washed with water and dried.

On analysis the dyestuff is found to contain 1.05 atoms of organically bound chlorine for each azo group present in the dyestutl.

When applied to wool from a slightly acid dyebath the dyestutf yields olive shades possessing good fastness to washing.

Example 10 A solution of 50 parts of 2-chloro-5-nitrobenzene sulphonchloride in 75 parts of benzene is added, during 30 minutes, to a solution of 28.3 parts of the trisodium salt of 2-methylamino-6 (1':5-disulphonaphth-2-ylazo) 5- naphthol-7-sulphonic acid and 1 part of the disodium salt of dinaphthylmethane disulphonic acid in 200 parts of water, and the resulting mixture is stirred at a temperature between 25 and 30 C. until no further additions of sodium carbonate are required to maintain the pH of the mixture between 7 and 8. Sodium chloride is then added to precipitate the dyestuff, which is then filtered off, washed with water, then with acetone, and is finally dried.

The dyestufi so obtained dyes cotton, viscose rayon and woollen textile materials in orange shades which possess good fastness to washing.

Example 11 A solution of 22 parts of 2-chloro-5'-nitrobenzoyl chloride in 66 parts of toluene is added, during 2 hours, to a stirred solution of 28.3 parts of the trisodium salt of 2 methylamino 6 (1:5'-disulphonaphth 2-y1azo)-5- naphthol-7-sulphonic acid and 1 part of the disodium salt of dinaphthylrnethane disulphonic acid in 220 parts of water at a temperature of 35 C., and the mixture is then stirred at a temperature between 35 and 40 C. until no further additions of sodium carbonate are required to maintain the pH of the mixture between 7 and 8. Sodium chloride is added to precipitate the dyestuif, which is then filtered off, washed with a 10% aqueous solution of sodium chloride, and dried.

The dyestutf so obtained dyes cotton, viscose rayon and woollen textile materials in orange shades which possess good fastness to washing.

Example 12 A solution of 25 parts of 4-chloro-3-nitrobenzene sulphonylchloride in 50 parts of acetone is added, during 1 hour, to a stirred solution of 26.1 parts of the disodium salt of 1-(2:5-dichloro-4'-sulphophenyl) 3 methyl-4- (5 "-arnino-2"-sulphophenylazo) -5-pyrazolone in 200 parts of water at a temperature between 35 and 40 C., and the resulting mixture is then stirred for 2 hours at this temperature. Sodium carbonate is added until the mixture is alkaline to litmus and sodium chloride is then added to precipitate the dyestuff which is filtered off, washed with acetone and dried.

The dye IStUlT so obtained dye-s cotton, viscose rayon and woolen textile materials in yellow shades which possess good fastness to washing.

The following table gives further examples of the new dyestufis of the invention which are obtained when the 28.3 parts of the trisodium salt of the azo compound used in Example 10 are replaced by equivalent amounts of the sodium salts of the azo compounds listed in the second column of the Table, and the 50- parts. of 2-chloro- S-nitrobenzene sulphornchloride used in Example 10 are replaced by equivalent amounts of the acid halides listed in the third column of the table, the reaction between the azo compound and the acid halides being carried out at 20 C. The fourth column of the table indicates the shades obtained when the dyestuffs are applied to textile materials.

Example A Compound Acid Halide Shade 13.. Z-amiuo-B-(2-sulphophenylazo)-5-naphth0l-7-sulphonic acid. 2-bromo-'5nitro-benzene Orange.

sulphonchloride.

14 1*(2':5'-dichloro-4'-sulphophenyl)-3methyl-4-(5-amino-2 .....(1 Yellow.

, sulphophenylazo)-5 pyrazolone.

15 2methylamino-6-(1:5-disulplionaphth-2-ylazo) 5-naph- -d0 Orange.

thol-7-sulphonlc acid.

16 do 4-bromo3-nitro-benzene Do.

sulphonchloride.

17 2-amino-6-(2-sulpl10phenylazo) 5-naphth01-7-sulphonic acid. d0 Do.

18 l-(2:5rdichlor0-4-sulph0phenyl)-3-methyl-4-(5 ami110-2- do Yellow sulphophenylazo)-5-pyrazolone.

Example 19 A solution of 21.6 parts of the disodium salt of 2- amino-6 (2-sulphophenylazo)-5-naphthol 7 sulphonic acid in 250 parts of water at a temperature of 60 C. is added to a suspension of 32 parts of 4-chloro-3-nitr'obenzene sulphonchloride in a mixture of parts of acetone and 125 parts of water, and the resulting mixture is stirred for 2 hours at 60 C. the pH of the mixture being maintained between 7 and 8 by the addition of sodium carbonate. Sodium chloride is then added to precipitate the dyestutf which is filtered ofi and dried.

The dyestufi so obtained dyes cotton, viscose rayon and woollen textile materials in orange shades which possess good fastness to washing.

Example 20 A solution of 14 parts of 4-chloro-3:S-dinitrobenzene sulphonchloride in 60 par-ts of acetone is added, during minutes, to a solution of 8.5 parts of the disodium salt of 2 amino- 6 (2-sulphophenylazo)-5-naphthol-7-sulphonic acid and 1 part of the disodium salt of dinaphthylmethane disulphon-ic acid in 150 parts of water and the resulting mixture is stirred at 30 C. until no further additions of sodium carbonate are required to maintain the pH of the mixture between 7 and 8. Sodium chloride is added to precipitate the dyestuff which is then filtered 01f, washed with acetone and dried.

The dyestufit' so obtained dyes cotton, viscose rayon and woolen textile materials in orange shades which possess good fastness to Washing.

Example 21 A solution of 12 parts of the disodium salt of 2-(4- amino-2'-acetylarninophenylazo)naphthalene 4:8 disulphonic acid in 120 parts of water is added to a suspen- 'sion of 15 parts of 4-chloro-3-nitrobe'nzene sulphonchlo ride in a mixture of 12 parts of acetone and 60 parts of water, and the resulting mixture is stirred for 3 hours at 20 C., the pH of the mixture being maintained at 7 by the addition of sodium carbonate. Sodium chloride is added to precipitate the dyeatufl, which is then filtered off, washed with acetone and dried.

The d'yestufi so obtained dyes cotton, viscose rayon and woolen textile materials in orange shades which possess good :fas'tne'ss to washing.

Example 22 To a solution of the mixed 1:2-chromium and cobalt complexes of 2 amino-6-(2'-hydroxy-4-sulpho-6-nitronaphth-l-y1azo)-5-naphthol-7-sulphonic acid [which is obtained by heating a solution of 13.62 parts of Z-amino- 6 (2'-hydroxy-4'-sulpho-6-nitronaphth-l-ylazo)5-naphthol-7-sulphonic acid in 75 parts of water with chromium acetate and cobalt acetate at 100 C.], there are added 5 parts of sulphonated oleic acid and a solution of 32 parts of 4-c-hloro-3-nitrobenzene sulphonchloride in 50 parts of benzene. The resulting mixture is stirred at 20 C. until no further additions of sodium carbonate are required to maintain the pH of the mixture between 6.5 and 7. Sodium chloride is then added to precipitate the dyestufif, which is filtered off, washed with benzene and dried.

The dyestuif so obtained dyes cotton, viscose rayon and woolen textile materials in black shades which possess good fastn'ess to washing.

Example 23 A solution of 5.8 parts of 4-bromo-3-nitrobenzene sulphonchlori-de in 20 parts of acetone and 50 parts of a N aqueous solution of sodium carbonate are simultaneously added, with stirring, to a solution of 5 parts of 4-amino-2'-hydroxy-5'-methylazobenzene in a mixture of 200 parts of acetone and parts of Water at a temperature of 5 C., and the resulting mixture is then stirred for 16 hours at 5 C. The precipitated dyestutf is then filtered off, washed with water and dried.

The dyestuif so obtained, when dispersed in aqueous medium, dyes polyarnide and polyethyleneterephthalate textile materials in yellow shades which possess good fastness to washing.

Example 24 A solution of 102 parts of 4-chloro-3-nitrobenzene sulphonchloride in 200 parts of benzene is added to a solution of 36.3 parts of the disodium salt of l-arnino-8- naphthol-3:6-disulphonic acid and 0.5 part of the disodium salt of dinaphthylmethane disulphonic acid in 500 parts of water at 25 C., and the mixture is stirred at a temperature between 25 and 30 C. until no further additions of sodium carbonate are required to maintain the pH of the mixture between 7 and 8. 50 parts of sodium carbonate are then added, the mixture is cooled to 0 C., and an aqueous solution of tetrazotised benzidine (which is obtained by tetrazotising 9.2 parts of benzidine by known methods) is added. The resulting mixture is stirred for 2 hours at 5 C., sodium chloride is then added to precipitate the dyestufi which is filtered oil and dried. When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuif yields blue shades which possess good fastness to Wet treatments.

Example 25 Cotton cloth is padded through an aqueous solution containing 2% by weight of the trisodium salt of. 6-(4"- chloro-3"-nitrobenzene sulphon)-methylamido 1 hydroxy- 2:2 azonaphthalene-l:3:5 trisulphonic acid, dried and then padded through an aqueous solution containing 1% by weight of caustic soda and 30% by weight of sodium chloride. The cloth is then steamed for 5 minutes and scoured at the boil in soap solution to remove unfixcd dyestuli.

An orange dyeing of excellent fastness to Washing and to light is obtained.

Example 26 Viscose rayon cloth is padded through an aqueous solution containing 2% by weight of the trisodium salt of 6-(4"-chloro-3' 5 "-dinitrobenzencsulphon) methylarnldo- 1-hydroxy-2:2'-azonaphtha1ene-1:3 :5 trisulphonic acid and 1% by Weight of sodium bicarbonate. The cloth is dried, steamed for 5 minutes and scoured at the boil in soap solution to remove unfixed dyestuif.

An orange dyeing of excellent fastncss to washing is obtained.

1 7 Example 27 A printing paste containing 1 part of the dyestufi used in Example 26, 35 parts of a aqueous solution of sodium alginate, 1 part of sodium bicarbonate and 5 parts of urea in 58 parts of Water is applied to cotton [fabric by roller and the fabric is dried, steamed tfor 1 minute then scoured in boiling soap solution to remove unfixed dyestuff.

An orange and white pattern is obtained in which the coloured portion is fast to washing and to light.

What We claim is:

1. Dyestuffs of the formula:

D is a chromophoric group selected from the class consisting of azo, anthraquinone, and phthalocyanine chromophoric groups;

R represents a member selected from the class consisting of hydrogen and lower alkyl;

Y represents a halogen atom selected from the class consisting of chlorine, and bromine; t-he N-H40g and NO groups are attached to the benzene ring at the positions ortho and para to the halogen atom represented by Y;

wherein m is one of the numbers 1 and 2;

and

n is one of the numbers 1 and 2.

2. Dyestuffs according to claim 1, wherein D contains a water-solubilizing group selected from the class consisting of sul-fonamido and sulfonic acid radica References Cited in the file of this patent UNITED STATES PATENTS 2,023,591 Hitch et a1. Dec. 10, 1935 2,150,787 Sohultis et a1. Mar. 14, 1939 2,254,602 Fleischhauer et a1. Sept. 2, 1941 2,714,590 Frisch et a1. Aug. 2, 1955 2,906,747 Wolfrum Sept. 29, 1959 2,957,863 Woltrum et a1. Oct. 25, 1960 2,959,582 Schimmelsohmidt et a1. Nov. 8, 1960 2,973,351 Montrnollin et a1. Feb. 28, 1961 2,993,885 Fasciati July 25, 1961 FOREIGN PATENTS 278,422 Germany Ian. 7, 1928 338,672 Great Britain Nov. 27, 1930 705,779 Germany May 9, 1941 OTHER REFERENCES Conant & Blatt, The Chem. of Org. Comp, 4th edition, The MaoMillan C0., pp. 136137. 

1. DYESTUFFS OF THE FORMULA: 